dissertation of final year research project ii submitted in ...improvement ofcold filter plugging...
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Improvement of Cold Filter Plugging Point of Jatropha-Corn Biodiesel
Blend Using Acrylic Copolymer
By
Ho May Yun
11122
Dissertation
of
Final Year Research Project II
submitted in partial fulfillment of
the requirements for the
Bachelor of Engineering (Hons)
Chemical Engineering
May 2012
Universiti Teknologi PETRONAS
Bandar Seri Iskandar
31750 Tronoh
Perak Darul Ridzuan
CERTIFICATION OF APPROVAL
Improvement of Cold Filter Plugging Point ofJatropha-Corn Biodiesel
Blend Using Acrylic Copolymer
Approved by,
by
Ho May Yun
A project dissertation submitted to the
ChemicalEngineeringProgramme
Universiti Teknologi PETRONAS
in partial fulfilmentofthe requirementfor the
BACHELOR OF ENGINEERING (Hons)
(CHEMICAL ENGINEERING)
Assoc Prof DrSuzana YusupDirector
^Y Green Technology^-^Mission Oriented Research (MOR)
-rjnJrcrsftHtknoloeiPETRONAS
(APTDR, SUZANAYUSUP)
UNIVERSITI TEKNOLOGI PETRONASTRONOH, PERAK
May 2012
CERTIFICATION OF ORIGINALITY
This is to certify that I am responsible for thework submitted inthisproject, that the originalworkis my ownexcept as specifiedin the references andacknowledgements, andthat theoriginal work contained herein have notbeen undertaken ordone by unspecified sources orpersons.
HO MAY YUN
in
ABSTRACT
Theaim of this study is to investigate the influence of fatty acid compositions in
biodiesel on some parameters such as theoxidation stability, iodine value and cold flow
properties. Edible oil is represented byrefined corn oil and non-edible oil represented by
jatropha curcas oil. In order to overcome the shortcomings of jatropha-corn biodiesel,
acrylic copolymer is introduced as a Cold Flow Improvers (CFIs) additive to reduce the
cold filter plugging point (CFPP). Crude jatropha oil was pre-treated to minimize the
high free fatty acid content. The treated jatropha oil and refined corn oil were then
transesterificated using sodium methoxide,CH3ONa as catalyst at standard reaction
conditions (reaction time, 1.5 h; weight of catalyst 1 wt.% of initial oil weight; molar
ratio methano:oil/ 6:1; reaction temperature, 64°C) to produce jatropha methyl ester
(JME) and corn methyl ester (CME) respectively. The biodiesel is then blended at
different mass ratios. Each jatropha-corn biodiesel blend parameters such oxidation
stability, iodine value, density, calorific value, fatty acid content and cold flow
properties are investigated. The biodiesel was tested accordingly to the standard UNE-
EN 14214 for quality assurance. Results show that ratio blend CME:JME (20:80) gives
6.42 hours of oxidation stability and -2°C for CFPP which complies with the EN 14214
standards. Acrylic copolymer as CFI is then added to the same blend ratio to reduce the
CFPP. CFI successfully reduced the CFPP from -2°C to -6°C which gives better cold
flow properties to the corn-jatrophabiodiesel blend.
iv
ACKNOWLEDGEMENTS
I wish to express my utmost appreciation to all who have contributed to the
success of this research project.
First and foremost, I would like to express my sincere gratitude to my supervisor
AP Dr. Suzana Yusup from Chemical Engineering Department, UTP, for her guidance
and support throughout the research project.
Heartfelt gratitude goes to Universiti Teknologi PETRONAS (UTP) for all the
resources; references books, online journals, and articles which have been helpful in
completing this report. The learning experiences were indeed worthwhile.
My gratitude is also extended to our FYP II coordinators, Dr. Norhayati Mellon
and Pn. Asna M. Zain for frequently arranging seminars, adjunct talks and providing
materials and documents in order to help us in completing the project. Ample time was
also given for us to complete the whole project.
I also would like to thank Miss Suliana bt. Abu Bakar for being supportive and
helpful as a postgraduate student throughout the entire project period.
Further thank is also extended to my family members for their moral support and
care.
Last but not least, I would like to thank God Almighty for His blessings and by
granting the will to complete the research project successfully and on time. Thank you.
TABLE OF CONTENT
CERTIFICATION OF APPROVAL ii
CERTIFICATION OF ORIGINALITY iii
ACKNOWLEDGEMENTS v
CHAPTER 1 1
INTRODUCTION 1
1.1 BACKGROUND OF STUDY 1
1.2 PROBLEM STATEMENT 2
1.3 OBJECTIVE 3
1.4 SCOPE OF STUDY 3
CHAPTER 2 4
2.1 CORN ZEA MAYS OIL 5
2.2 JATROPHA CURCAS L. OIL 5
2.3 TRANSESTERIFICATION 6
2.4 IODINE VALUE (IV) 7
2.5 OXIDATION STABILITY 8
2.6 COLD FLOW PROPERTIES 9
2.6.1 Cold Flow Improver (CFI) 11
CHAPTER 3 13
METHODOLOGY 13
3.1 MATERIALS 13
3.2 EQUIPMENT 14
3.3 EXPERIMENTAL PROCEDURE 15
3.3.1 Pre-Esterification 15
3.3.2 Transesterification 15
3.4 ANALYTICAL METHODS 17
3.4.1 Acid Value 17
3.4.2 Fatty Acid Composition 18
vi
3.4.3 Density
3.4.4 Oxidation Stability
3.4.5 Cold Flow Properties
CHAPTER4
4.1 CALCULATIONS FOR BIODIESEL PREPARATION 19
4.1.1 Pre-esterification of Crude Jatropha Oil 19
4.1.2 Transesterification of Treated Jatropha Oil/Refined Corn Oil 20
4.2 CHARACTERIZATION OF BIODIESEL SAMPLES 21
4.2.1 Titration for Acidity Value 21
4.2.2 General Quality Parameters 22
4.2.3 Fatty Acid Compositions 23
4.3 IODINE VALUE 25
4.4 OXIDATION STABILITY 26
4.5 Cold Fiter Plugging Point 28
4.5.1 Improvement of CFPP by blending of JME and CME 28
4.5.2 Performance of Acrylic Copolymer as ColdFlow Improver (CFI) 29
CHAPTER 5 31
REFERENCES 32
APPENDIX 35
APPENDIX A 35
APPENDIX B 36
VII
LIST OF FIGURES
Figure 2.1 : Transestrification processFigure 2.2 : Cloud Point, Cold Filter Plugging Point and Pour PointFigure 2.3 : A polymethacrylate moleculeFigure 3.1 : Pre-esterification and Transesterification Experimental SetupFigure 3.2: Transesterification processFigure 4.1 : Metrohm 873 Biodiesel RancimatFigure 4.2: Oxidation Stability ofJatropha/Corn Biodiesel BlendFigure 4.3 : Automatic tester ISL FPP 5GsFigure 4.4: CFPP of JME:CME blendFigure 4.5: Effects of Acrylic Copolymer on CFPP in CME:JME/20:80 BlendFigure Bl: Comparison of the Induction Period of the BlendsFigure B2: Induction Period at CME:JME (100:0)Figure B3: Induction Period at CME:JME (80:20)
Figure B4: Induction Period at CME:JME (60:40)
Figure B5: Induction Period at CME:JME (40:60)Figure B6: Induction Period at CME:JME (20:80)Figure B7: Induction Period at CME:JME (0:100)
LIST OF TABLES
Table 2.1 : Weighting Factors for Common Fatty Acids to Determine Iodine ValueTable 1.1: Materials required for Acidity CheckTable 3.2: Materials and required for Pre-esterificaton reactionTable 3.3: Materials required for Transesterification reactionTable 3.4: Materials required for addition of cold flow improversTable 4.1 : Acidity Value TestTable 4.2 : General quality parameters of biodieselTable 4.3 : Chemical structures of common fatty acidsTable 4.4 : Neat jatropha methyl ester and neat corn methyl ester major fatty acidcomponent
Table 4.5 : Fatty acid compositions of jatropha methyl ester(JME) and corn methylester(CME) with its respective blend ratiosTable 4.6 : Weighting Factors for CommonFatty Acids to Determine Iodine ValueTable 4.7: Fatty acid composition in total of saturated, monounsaturated andpolyunsaturated with iodine valueTable 4.8 : Iodine value
Table Bl: Acidity of Crude Jatropha OilTable B2: Acidity of Refined Corn OilTable B3: Acidity for Treated Jatropha OilTable B4: Cloud Point Runs
Table B5 : Pour Point Runs
Table B6 : CFPP Run
vni
CHAPTER 1
INTRODUCTION
1.1 BACKGROUND OF STUDY
The world's total energy supply comes mainly from petroleum, coal and natural gas.
Prediction of worldwide petroleum reserves is ambiguous but the general prediction of
maximum production in or before the period 2010-2020 will be decline to the 1960 level by
the year 2050. Consequently, the world can no longerafford to rely merely on fossil oil and
the bestway is to maintain energy reliability is through diversity in sources of energy (Bart,
Palmeri, & Cavallaro, 2010). Recently in Malaysia, the Renewable Energy (RE) act is
established to meet the 40% carbon emission intensity reduction target by 2020 (Invest
Malaysia). Many countries such as Europe have raised their share of renewable energy to 6-
10%, expected to increase to 20% by the year 2020(Ibrahim, 2012). Biodiesel can be one of
the alternative fuels to the current market concentration of oil supply and potentially
improves the environmental aspect (Wetzstein & Wetzstein, 2011).
There are several types of biodiesel. The first typeof biodiesel is derived from vegetable oil
mainly from food crops. Biodiesel can also be made from animal fat can be raw, processed
or used. The second type is liquid fuels which can be derived from biomass such as ethanol.
At present, large-scale biodiesel production relies on plantation crops as feedstock due to
the existing needs of food supply in agricultural industry.
Nevertheless, there are debates over the increase of food prices alongside with the increase
of global biofuel production. Studies suggested that biofuel production does have a modest
3% to 30% of contribution to the growth in the commodity food prices perceived in
2007/2008 (Mueller, Anderson, & Wallington, 2011). The increase of food prices continues
to affect the poorer countries, therefore, the competition of edible crops for biofuel
production and food supply is not ideal (Gui, Lee, & Bhatia, 2008). One of the ways to
overcome the food prices crisis is to use non-edible oils for biodiesel production instead
(Sims, Mabee, Saddler, & Taylor, 2010).
1.2 PROBLEM STATEMENT
One of the main setbacks related with the use of biodiesel at cold climates are operability
problems in diesel engines when high amount of saturated fatty acid methyl ester
components clogged fuel lines and filters when solidified(Boshui, Yuqiu, Jianhua, Jiu, &
Jiang, 2010). Most non-edible oils contained more saturated fatty acid in the range of C]6-
Cis. Meanwhile, edible oils that contained more unsaturated fatty acids are prone to
oxidation but have good low temperatures properties (Das, Bora, Pradhan, Naik, & Naik,
2009).
Over the last few years, several ways has been studied to resolve the low-temperature
problems of biodiesel. These include the blending of biodiesel with conventional diesel
fuels, winterization, adding additives and blending with branched-chain esters. Of all
methods, chemical additives was seems to be convenient and economical, and thereby the
most attractive (Boshui et al., 2010). The aim of this work deals with the correlation of fatty
acid methyl ester composition with important parameters; such as the oxidation stability,
CFPP and iodine value (IV) of the biodiesel. As an effort to promote the usage ofnon-edible
oil as feedstock in biodiesel production, an investigation of the blending of methyl ester
from non-edible oils and methyl ester from edible oil is done. In this study, edible oil
represented by refined corn oil and non-edible oil represented by jatropha curcas oil. In
order to overcome the shortcomings of jatropha-corn biodiesel, acrylic copolymer is
introduced as CFI to further reduce the CFPP.
1.3 OBJECTIVE
The main objectives of this research project are as the following;
i. To produce methyl ester from jatropha curcas L. oil and refined corn oil
ii. To blendjatropha curcas L. methyl ester and refinedcorn oil methyl ester; and obtain
the best blend that achievedoxidation stability of 6 hours and parameters such as iodine
value and cold flow properties that complies with EN14214 standards,
iii. To observe and investigate the effectiveness of commercial CFI in enhancing the cold
flow properties ofjatropha-corn methyl ester
1.4 SCOPE OF STUDY
In this project, the study aspects are the cold flow properties, oxidation stability and iodine
value of the biodiesel blend. The scope of study includes three main parts. The first one is
the production of corn methyl ester (CME) and jatropha curcas L. methyl ester (JME)
followed by the blending of both biodiesel as the following mass ratios :
i. CME:JME (0:100)
ii. CME:JME (20:80)
iii. CME:JME (40:60)
iv. CME:JME (60:40)
v. CME:JME (80:20)
vi. CME:JME (100:0)
The secondpart is the study of relation between fatty acid methyl ester compositions of each
blend with oxidation stability, iodine value and CFPP. The third part is the investigation of
CFPP before and after the addition of acrylic copolymer at several concentrations;
0.0mass%, 0.5mass% and 1.0mass%.
CHAPTER 2
LITERATURE REVIEW
Vegetable oil comprises of 98% triglycerides and a small amount of monoglycerides and
diglycerides(Ayhan, 2009). Triglycerides have one glycerol with three fatty acids. Direct
usage of triglycerides in diesel engine is discouraged due to its long molecule chains and
highly viscous characteristic (£aynak, Giiru, Bicer, Keskin, & icingur, 2009). Efforts have been
given in finding ways to reduce the viscosity of vegetable oils. Methods that were
discovered to reduce the viscosity are: dilution (blending) with hydrocarbons,
microemulsification, pyrolysis or thermal cracking, catalytic cracking and
transesterification(Schwab, Bagby, & Freedman, 1987).
Transesterification is the mostconventional method where reaction between triglyceride and
alcohol with the presence of catalyst gives biodiesel or fatty acid alkyl ester (FAME) and
gylcerols. Biodiesels are suitable to replace diesel fuel without any modification of engines
hardware. One study on the life cycle assessment (LCA) shows biodiesel is more
environmentally friendly than the diesel based on the global warming and renewable energy
aspect scores of biodiesel and diesel production (Jinglan).
Comparatively to the making of diesel fuel, diesel fuel is processed from fossil fuel through
fractional distillation. Extracted crude oil contained different hydrocarbon compounds that
are separated through difference in boiling point. Diesel is separated from the crude oil
when the distillation chamber reaches 200°C to 350°C in temperature (Leffler, 2008).
Biodiesel on the other hand, is biodegradable and have environmental benefits as it rarely
contain sulfur(Balat & Balat, 2008).
2.1 CORN ZEA MAYS OIL
Corn oil was ever considered as a biodiesel fuel in 1952. However, due to its relatively
expensive and high values as edible oil, biodiesel made from corn oil is not economically
feasible. Corn is the third most vital grain in the world after wheat and rice. It is the most
extensively used cooking oil in the US as a fast food frying oil. Corn oil's benefits include
its very low level of linolenic acid, high level of unsaponifable and stabilityduring frying. It
also has a mild nutty flavor, contain high amount of unsaturated fatty acids and low content
of saturated fatty acids (Bart et al., 2010).
2.2 JATROPHA CURCAS L. OIL
There is a growing in jatropha curcas L. as a biodiesel to help alleviate the energy crisis,
reduce the countries dependence on foreign imports and generates income in rural areas of
developing countries. The estimates of the oil content in seeds range from 35-40% and in
the kernels 55-60%. Many developing countries cannotafford to use edibleoils as an energy
source because they are already in short supply.Thus, non-edibleoils from under researched
plants such as Jatropha, Pongamia, Neem, Kusum and Pilu are being advocated (Wright &
Evans, 2008). Of the above Jatropha is considered the most potential source as non-edible
biodiesel producing plant because it can be grown on almost any soil type. Jatropha curcas.
L oil contain high free fatty acid (FFA) content and requires acid-catalyzed esterification.
2.3 TRANSESTERIFICATION
Transesterification (alcoholysis) is an equilibrium reaction and occurs essentially by mixing
the reactants (Schwab et al., 1987). Transesterification occur when triglyceride (vegetable
oil) reacts with an alcohol (methanol) in the presence of a strong acid or base catalyst
(Figure 2. l)(Ma&Hanna, 1999).
CH2-OOC-R,
CH-OOC-R2 +l
3R'OH
CatalystR,-COO-R'
R2-COO~R'
CH2-OH1
+ CH-OHi
l
CHrOOOR, R3-COO-R'i
CH2-OH
Glyceride Alcohol Esters Glycerol
Figure 2.1 : Transestrification process (Ma & Hanna, 1999).
In biodiesel production, the choice of acid and alkali catalyst can varied depending on the
free fatty acid (FFA) content in the raw vegetable oil. During the reaction, FFA may react
with alkali catalyst to form soap and water which deters the ester formation (Ayhan, 2009).
Therefore, alkali catalyst reaction should not exceed the recommended limit of acidity value
(2mg KOH/g oil) and FFA (1%) to avoid deactivation of catalyst, formation of soaps and
emulsion. This decreases the final yield of ester and consumes alkali. High FFA needs two-
step transesterification process, acid transesterification followed by alkali-transesterification
to get high biodiesel yield (Keskin, Guru, & Altiparmak, 2008; Patil& Deng, 2009). Methanol is
preferable as the solvent comparatively to ethanol because of it is a polar short chain alcohol
that is low in cost. Alkali catalyst, potassium methoxide effects complete transesterification
more quickly than sodium methoxide, CH3ONa at equivalent molar concentration with the
same triglyceride samples. Due to the danger possess in metallic potassium handling,
sodium methoxide, CHsONa is preferable (Ayhan, 2009).
2.4 IODINE VALUE (IV)
Iodine value is used for the determination of the quality of diesel fuel derived
from vegetable oil. Denote as grams of h absorbed/lOOg sample under standard conditions,
the iodine value is a degree of the unsaturation of oils and fats and their fatty acid
derivatives, which can be determined in many different methods. There are many methods
used to determine iodine value. One of the methods used is the American Oil Chemist'
Society (AOCS) method Cd ld-92 (Balat & Balat, 2008). The test begins with O.lgm of
tested oil taken in to 250ml of glass stopper iodine flask. The oil is dissolve in 20ml of
carbon tetrachloride and 25ml of Wij's solution. The contents of the flask are shaken well
and are placed in the dark for half an hour. At the end of this time 20 ml of 15% potassium
iodide solution is added followed by the addition of 100ml of distilled water. The contents
are then titrated against 0.1N sodium thiosulfate, Na2S203.5H20 using starch as indicator
until the yellow iodide color disappeared. The solution is again titrated until the
disappearance of color. Same procedure was done for blank solution. Iodine value was then
calculated by the following formula.
(Blank titration —Sample titration) x Normality of Na2S203.5H20 x Equivalent weight of iodineSample weight (gram)
Where,
Normality of sodium thiosulfate, Na2S203. SH20 = 0.1
Equivalent weight of iodine = 127
According to EN-14214 for determination of the iodine number the mass percentage of
the fatty acid methyl esters is multiplied by an assigned weighting factor. In this project,
the EN-14214 method is used. Table 2.1 shows the weighting factors for each fatty acid
composition.
Table 2.1: Weighting Factors for Common Fatty Acids to Determine Iodine Value(EN 14214:2003)
Methyl Ester Formula Factor
Saturated fatty acids Cn:0 0
Palmitoleic C16:l 0.950
Oleic C18:l 0.860
Linoleic C18:2 1.732
Linolenic C18:3 2.616
Gadoleic C20:l 0.785
Erucic C22:l 0.723
2.5 OXIDATION STABILITY
The oxidation stability of biodiesel differs extensively on the source of oil where
the biodiesel is derived, processing conditions, contaminants particularly trace metals, water,
radicals and peroxides and storage stability can be influence by humidity, sunlight,
microorganisms, temperature, oxygen and presence of organic occurring stabilizers (Bart et
al., 2010). Oxidation can form volatile small-chain fatty acids, which can lead to corrosion
in the engine. Meanwhile, polymers can formed, which agglomerates as "gums" which may
cause deposition of residue in the engine. Oxidation involves both storage and thermal
stability. The oxidation stability is determined via the Rancimat method. This test is based
on the period of time where methyl ester aged under constant air flow. When there is an
increase of conductivity of deionized water contained in the reservoir, it retains the volatile
acid liberated during the oxidation of fatty material. More volatile acids dissociates when
methyl ester deteriorates rapidly. According to European Committee for Standardization, an
oxidation curve is obtained when the conductivity is recorded continuously and this is
known as the IP or oil stability index. The European standard EN14112 establishes that the
oxidative stability of biodiesel should be determined at 110°C and required a minimum
value of 6 hours for the induction period (Dantas et al., 2011).
2.6 COLD FLOW PROPERTIES
In the previous study on optimization of biodiesel from edible and non-edible vegetable oil,
the jatropha and corn methyl ester show similar fuel properties to conventional diesel
compare to canola and karanja methyl ester(Patil & Deng, 2009). One of the disadvantages
of biodiesel is poor temperature operability, along with inferior oxidative and storage
stability, lower volumetric energy content, and higher nitrogen oxides exhaust
emissions(Joshi, 2011). Biodiesel with high unsaturated ester content show better cold flow
properties but have lower oxidation stability(Patil & Deng, 2009;Garcia-Perez, Adams,
Goodrum, Das, & Geller, 2010). Saturated fatty acid in the range of Cie-Cis has high
oxidation stability while unsaturated fatty acids, such as oleic and linolenic, are prone to
oxidation(Das et al., 2009).The biodiesel that has higher level of saturated methyl ester has
higher cetane number however it is susceptible to the free-radical attack(Knothe, Krahl, &
Van Gerpen, 2005).
Biodiesel with poor cold flow properties tend to cause formation of micro solid wax crystal
nuclei at low temperatures. As temperature decrease further, these crystal starts to grow
visibly and known as the cloud point (CP). At temperature below CP, larger crystals fuse
together to form large agglomerates that tend to cut off flow through fuel pipes and filters
causing start-up difficulties (Knothe et al., 2005). The temperature at which fuel crystals
have agglomerated in sufficient amounts to cause a test filter to plug is the CFPP. Pour point
is the temperature at which the fuel contains so many agglomerated crystals it is essentially
a gel and will no longer flow. The definition of CP, PP and CFPP is as the following and
illustrated in Figure 2.2;
i. Cloud Point: The temperature at which the first appearance of small solid crystals visibly
when observed as the fuel is cooled (D 2500).
ii. CFPP: The lowest temperature at which 20ml of sample safely passed through the filter
(wire mesh filter screen) under vacuum within 60 sec (EN 116) (Fernandez, Ramos, Perez, &
Rodriguez, 2010).
iii. Pour Point: The temperature at which the fuel is fully agglomerated, become gel-like and
will no longer flow when pour (D 97).
Numerous researches on the improvement of cold flow properties in biodiesel were carried
out. Biodiesel mixed with regular petroleum diesel at various ratio reduced CP and CFPP
{Kleinova, Paligova, Vrbova, Mikulec, & Cvengros, 2007 ; Knothe et al., 2005). Winterization
technique such as crystallization Alteration with methanol is used to improve the cold flow
properties of peanut biodieseI(Perez, Casas, Fernandez, Ramos, & Rodriguez, 2010). By adding
CFIs as fuel additives into soybean diesel, olefin-ester copolymers (OECP) were found to
reduce PP and CFPP(Boshui et al., 2010).
There are also a study on Differential Scanning Calorimetry(DSC) mixing bio-oil and
biodiesel shows improvement on oxidation stability. Bio-oil contain hindered phenols and
nano-particles of oligometric that modify crystal behavior by inhibiting wax crystals from
growing and subsequently improving the cold flow of soybean diesel (Garcia-Perez et al.,
2010).Metallic-based additive; magnesium, nickel and manganese is added into biodiesel
and resulted in decrease of viscosity, flash point and pour point effectively as well as
greenhouse gases emission reduction(GUru, Koca, Can, Cinar, & §ahin, 2010; Keskin, Guru, &
Altiparmak, 2007; Qaynak et al., 2009). A study on ethyl levulinate, an inexpensive bio-based
additive appears to be an acceptable CFI for biodiesel with high saturated fatty acid content
such as cottonseed methyl ester(Joshi, Moser, Toler, Smith, & Walker, 2011).
Evidently, extensive work has been done on the flow properties of biodiesel production;
however less significant work has been done concerning the improvement of cold flow of
blended methyl ester from different sources of oil. One of the study on the blend of jatropha
and palm methyl ester had achieved improvement in oxidation stability, and resulted in
reasonable cold flow properties that are suitable for tropical climate but not for production
ofwinter grades diesel fuels (Sarin, Sharma, Sinharay, & Malhotra, 2007).
10
Figure 2.2 : Almost clear appearance of biodiesel after cloud point test (left),
Cloudy appearance of biodiesel after CFPP test (middle), Fully crystallized after
pour point test (right)
2.6.1 Cold Flow Improver (CFI)
One research reported the evaluation on the effectiveness of CFI in different
blended biodiesel (Echim, Maes, & Greyt, 2012). High saturated methyl esters,
such as tallow, palm, chicken and jatropha methyl ester were blended with high
level of unsaturated methyl ester such as soybean and rapeseed biodiesel samples
followed by the usage of CFI. However, there were no blend on jatropha methyl
ester and corn methyl ester was made. CFPP of the biodiesel blends were
improved when CFI were added (Echim et al., 2012). Hence, the aim of this
study is to investigate the potential of acrylic copolymer as CFI to further
improve the cold flow properties of jatropha-corn methyl ester blend. Another
advantage is to allow biodiesel works in winter conditions and to reduce the
dependency and usage of edible-oil.
CFI behave by hindering crystal growth, but do not prevent crystal initiation.
They have little effect on the temperature at which crystals that has already form.
To be more precise, CFI co-crystallize on the edges of the growing crystal plates
when crystals form, thereby inhibiting the continued agglomeration of the
plate(Bart et al., 2010). The CFI results in smaller size of crystals (d = lOurn-
11
lOOum) enabling it to pass through filters without clogging (Knothe et al., 2005).
The impact on cold flow properties is that, while CP is little affected,
considerable improvements in CFPP and PP can obtained.
CFI are usually Pour Point Depressant (PPD) having low molecular weight
copolymers in similar structure and melting point to the n-alkane paraffin
molecules, allowing them to co-crystallize after nucleation has been initiated
(Knothe et al., 2005). Types of copolymer includes polymethacrylates,
polyalkylmethacrylat.es, copolymer of vinyl acetate-maleate esters and many
more (Knothe et al., 2005). Polymethacrylates are the most widely used pour
point depressants. R in the ester has a major effect on the product, and is usually
represented by a normal paraffinic chain of at least 12 carbon atoms that ensure
solubility is shown in Figure 2.3. Typically it has a molecular weight of 7000-
10000 number in average. Commercial materials normally contain mixed alkyl
chains which can be branched.
CH, 4COOR
CH3
Figure 2.3 : A polymethacrylate molecule
12
CHAPTER 3
METHODOLOGY
3.1 MATERIALS
Crude jatropha oil was procured from Eco Energy Solution Pty. Ltd. Refined corn oil was
Mazola/Sweet Yet Development Sdn. Bhd obtained from a local store. Anhydrous methanol
(99.8%), Sulphuric Acid reagent (95-98%) and Sodium Methoxide, CH3ONa (25% in
methanol solution) were obtained from Sigma-Alrich. Chemicals procured from Merck via
Avantis Laboratories Sdn. Bhd. were Toluene, Isopropanol and Anhydrous Sodium Sulfate.
Potassium Hydroxide and Phenolphthalein were obtained from R&M Chemicals and Fisher
Scientific respectively. All the chemicals used were analytical reagent grade. Tables 3.1-3-4
shows the materials required for each analytical methods.
Table 2.1 : Materials required for Acidity Check
Aspect Item Brand/Procured from
SolventToluene Merck/Avantis Laboratories Sdn. Bhd
Isopropanol Merck/Avantis Laboratories Sdn. Bhd
TitrantPotassium Hydroxide R&M Chemicals
IndicatorPhenolphthalein (General Purpose
Grade)Fisher Scientific
Table 3.2: Materials and required for Pre-esterificaton reaction
Aspect Item Brand/Procured from
OilRefined Corn Oil Mazola/Sweet Yet Development Sdn. Bhd.
Jatropha Curcas L. Oil Eco Energy Solution Pty. Ltd.Alcohol Methanol Sigma-Alrich 34940
Acid Sulphuric Acid Sigma-Alrich ACS Reagant 95.0% - 98.0%Drying Agent Anhydrous Sodium Sulfate Merck/Avantis Laboratories Sdn. Bhd.
Table 3.3: Materials required for Transesterification reaction
Aspect Item Brand/Procured from
OilRefined Corn Oil Mazola/Sweet Yet Development Sdn. Bhd.
Jatropha Curcas L. Oil Eco Energy Solution Pty. Ltd.Alcohol Methanol Sigma-Alrich 34940
CatalystSodium Methoxide (25%
solution in methanol)Sigma-Alrich /Avantis Laboratories Sdn.
Bhd.
Drying Agent Anhydrous Sodium Sulfate Merck/Avantis Laboratories Sdn. Bhd.
13
Table 3.4: Materials required for addition of cold flow improver
Aspect Item Brand/Procured from
OilRefined Com Oil Mazola/Sweet Yet Development Sdn. Bhd.
Jatropha Curcas L. Oil Eco Energy Solution Pty. Ltd.Additive Acrylic Copolymer Viscoplexl0-330/Platinum Energy Sdn. Bhd
3.2 EQUIPMENT
Esterification of crude jatrophaoil and transesterification ofjatrophaoil and refined corn oil
were carried out in a 250ml three-necked round bottom flask place in a water bath. The
reactor was equipped with a reflux condenser, to avoid the evaporation of methanol;
magnetic stirrer for rigorous stirring; and a heating plate for a constant heat supply (Figure
3.1).
Figure 3.1 : Pre-esterification and Transesterification Experimental Setup
14
3.3 EXPERIMENTAL PROCEDURE
3.3.1 Pre-Esterification
Acid-catalyst pretreatment was carried out since the initial acid value of
crude jatropha oil was 23.41% or 47 mg KOH/g oil. Refined corn oil yield an
acidic value of 0.79% which is lower than 1%, thus, pre-esterification for refined
corn oil is not required. 250g of Crude Jatropha Curcas L. Oil was taken in a
three-necked round bottomed flask where 88 g of methanol was taken in a 200
ml measuring cylinder. 2.5g (1.0 wt%) of sulfuric acid (FLSO4) was measured
and poured drop wise into a measuring cylinder containing the methanol. Oil
was warmed by placing the round-bottomed flask in the water bath maintained at
64°C. Methanol and sulfuric acid were added into the oil for vigorous mixing by
means of a mechanical stirrer fixed in the flask. The required temperature (64°C)
was maintained throughout the stirring and after 4 hours, the mixture was left
overnight. The 2 layer mixture of treatedjatropha oil and residue are then poured
into a separating funnel and the bottom layer (treated jatropha oil) is separated
and stored. Treated jatropha oil is washed with de-ionized water to further
remove impurities. The residual methanol and water were separated from the oil
by rotary evaporation under vacuum at 70°C for 30minutes. Finally, treated
jatropha oil is swirled with anhydrous NaS04 to remove traces of moisture and
then separated from the anhydrous via gravitational filtration. Acidity value test
is repeated to ensure reduction of acidic value to less than 1 mg KOH/g oil.
3.3.2 Transesterification
200g of refined corn oil was taken in a three-necked round bottomed flask.
46.88 g of methanol was taken in a 200 ml beaker. 2 g of sodium methoxide,
CFbONa was taken in a measuring cylinder. The oil was warmed by placing the
round-bottomed flask in the water bath maintained at 64°C to avoid the
evaporation of methanol. Sodium methoxide, CFbONa and methanol solution
was added into the oil for vigorous mixing by means of a mechanical stirrer
fixed in the flask. The required temperature (64°C) was maintained throughout
15
the stirring and after 90 minutes. Mixture is then poured into a separating funnel
and leaves it overnight. The 2 layer mixture of refined Corn biodiesel (CME) and
the bottom layer (glycerol) is separated. CME is washed with de-ionized water
carefully to further remove impurities (e.g catalyst, glycerol). The residual
methanol and water were separated from biodiesel by rotary evaporation under
vacuum at 70°C for 30minutes. Finally, biodiesel is swirled with anhydrous
sodium sulfate, NaS04 to remove moisture. Mixture of CME and anhydrous
NaS04 is then separated by gravitational filtration to pure, crystal clear biodiesel.
Similar steps were repeated for treated jatropha oil to form jatropha biodiesel.
Figure 3.2: Transesterification process (1) Refined Corn Oil (2)
Transesterification (3) Separation of biodiesel and glycerol (4) Washing with
deionized water (5) Rotary Evaporator (6) Biodiesel as product
16
3.4 ANALYTICAL METHODS
3.4.1 Acid Value
Acid values (AV) of vegetable oil were determined according to American Oil
Chemists' Society (AOCS) Method Cd 3d-63. Before proceeding with
transesterification, the oil sample needs to be tested for acidity value. When an acid
value of 2.0mg KOH/g oil or less was achieved, the oil can be used in alkali
catalyzed transesterification reaction. When neat biodiesel is produced, acidity value
is again tested to obtain EN14104 requirement of 0.5mg KOH/g oil and below.
Titrant
Solvent
Indicator
KOH (85% Assay); 0.66g/500mL Isopropanol
Isopropanol: Toluene; (1:1)
Phenolphthalein; LOg/lOOmL Isopropanol
Fill burette with KOH titrant. Aliquot 25mL solvent into beaker with magnetic
stirrer and add 0.4 mL indicator. Note volume on burette. Add titrant drop-wise
while stirring until faint pink color remains. Note volume on burette and record
volume KOH used (B). Add 2g (W) of oil sample and mix until fully dissolved. Add
titrant drop-wise until faint pink color remains. Note volume on burette and note
volume KOH used (A). Acid Value is tabulated using the below equation:
[(A-B)xNx 56.11]Acid Value =
Where:
A = Volume of titrant used for sample
B = Volume of titrant used for blank
N =0.02
W=2
17
W
3.4.2 Fatty Acid Composition
The fatty acid composition at different blend ratios are analyzed by gas
chromatography on a 7890A GC system from Agilent Technologies, equipped
with Triple Axis inert XL El/Cl MSD detector and Quadrupole mass analyzer.
The scan rate is 125,000 amu/sec and the inlet has a direct insertion probe and
pyrolizer.
3.4.3 Density
Density meter Anton Paar DMA 4500M is used to measure the density of the
neat biodiesel. The conversion factor for the correction of density, determined by
EN ISO 3675 over a range of temperatures from 20°C to 60°C to density at 15°C
is calculated by the formula :
P(is)= p(n +0.723(r-15)
3.4.4 Oxidation Stability
The induction period (IP) of each biodiesel blend ratios was quantified using the
Metrohm 873 Rancimat instrument with the method EN14112 for the neat
biodiesel and its blends. In this method, 3g of sample were heated at 110°C
under constant air flow (10 L/h).
3.4.5 Cold Flow Properties
CP and PP of each neat biodiesel was measured using ISL CPP 5Gs using D2500
and D97 method respectively. An automatic tester ISL FPP 5Gs was used to
quantify the CFPP of neat biodiesel and each biodiesel blend ratios. Each test
required a 45ml of biodiesel sample.
CHAPTER 4
RESULT AND DISCUSSION
4.1 CALCULATIONS FOR BIODIESEL PREPARATION
4.1.1 Pre-esterification of Crude Jatropha Oil
The calculations of the amount of methanol, and the amount of catalyst used forpre-esterification of crude jatropha oil to produce treated jatropha oil are shown.The methanohoil ratio used is 10:1. Catalyst used is sulfuric acid (H2S04) at lwt%
of total oil used.
Mass ofcrude jatropha oil
Molecular weight ofjatropha oil
Moles ofjatropha oil
250g
910.23g/mol
Mass of jatrop ha oil
Molecular Weig ht of jatrop ha oil
250g
910.23g/mol
0.275mol
Mass of methanol =
Ratio of methanol: oil x Moles of jatropha oilx Molecular weight of methanol
MassofH2S04 =
10
= y x (°-275)x 32-04 = 88g
lwt% x Mass of jatropha oil
— x250g100 6
2.5g
19
4.1.2 Transesterification ofTreated Jatropha Oil/Refined Corn Oil
The calculations of the amount of methanol and the amount of catalyst used for
transesterification of com oil to produce com methyl ester are shown. The
methanohoil ratio of 6:1 is used with alkalized catalyst sodium
methoxide,CHsOMe at lwt% of total oil used. Same calculations were repeated
for treated jatropha oil to produce jatropha methyl ester.
Mass ofcorn oil
Molecular weight ofcorn oil
Moles of corn oil
200g
820.13g/mol
Mass of corn oil
Molecular Weight of corn oil
200g
820.13g/mol
0.244 mol
Mass of methanol =
Ratio of methanol: oil x Moles of corn oil x Molecular weight of methanol
= 7 x (0.244 )x 32.04 = 45.37g
Mass ofCH.OMe lwt% x Mass of corn oil
2.00#
20
4.2 CHARACTERIZATION OF BIODIESEL SAMPLES
4.2.1 Titration for Acidity Value
To avoid the formation of soap and loss of ester during alkaline catalyst
transesterification, acidity value titration was carried to identify the acidity value.
It is found that pre-esterification reaction is needed to be carried for crude
jatropha oil since an initial acidity value of 46.81 mg KOH/g oil or 23.41% FFA
was obtained. The acidity value greatly reduced to 1.40 mg KOH/g oil after the
pretreatment with sulfuric acid catalyst.
On the other hand, corn oil advanced to the transesterification reaction to form
CME since the acidity value scored 1.57 mg KOH/g oil or 0.79% FFA. It did not
exceed the maximum allowable specification at 2.0mgKOH/g oil or 1% FFA.
The acidity value of the neat biodiesel was examined again after
transesterification reaction. CME and JME met the EN14104 requirement. Table
4.1 shows the summarized results of the acidity value test.
Table 4.1 : Acidity Value Test
Acidity Value TestTest
MethodLimits
Average Acid Value(mg KOH/g oil)
JME CME
Initial Crude/Refined Oil - - 46.81 1.57
After Pre-esterification (Oil) - 2.0 max 1.40 1.57
After Transesterification EN14104 0.5 max 0.12 0.11
21
4.2.2 General Quality Parameters
Standards are vital for commercialization and market of biodiesel. The
European norm EN14214 sets specifications and test methods for biodiesel
(FAME) to be used as automotive fuel for diesel engines. The European
standard tends to be stricter than the American ASTM D6751 standard,
displaying more stringent limits. Table 4.2 shows some of the general properties
of the biodiesel to ensure a good quality assurance of biodiesel.
Table 4.2 : General quality parameters of biodiesel
Properties Test Method LimitsMethyl ester
JME CME
Ester Content (%) EN 14103 96.5 min 95.7 95.9
Cloud Point (°C) D2500 - 4 0.1
Pour Point(°C) D97 - 3 0
CFPP(°C) EN 116 +5 to -20 -1.2 -4
Density (kg/m3)at 15°C
EN ISO 3675 860 to 900 882.46 885.70
Acidity Value(mg KOH/g oil)
EN14104 0.5 max 0.12 0.11
Calorific Value
(MJ/kg)ASTMD240 - 39.75 39.82
22
4.2.3 Fatty Acid Compositions
Gas chromatography is used to analyze the fatty acid compositions of JME and
CME; also the fatty acid composition of each blend ratios. Table 4.3 shows the
common chemical structures of common fatty acids used to identify each
component obtained from the GC results. Table 4.4 is a comparison table where
the fatty acid components of this work are compared to available journal sources.
Table 4.3 : Chemical structures of common fatty acids(BarawaI & Sharma, 2005)
Fatty Acid Formulas Methyl Ester Terms
Myristic C14:0 Methyl tetradecanoic acidPalmitic C16:0 Hexadecanoic acid
Palmitoleic C16.-1 9-Hexadecenoic acid
Margeric C17:0 Heptadecanoic acid
Stearic C18:0 Octadecanoic acid
Oleic C18:l 9-Octadecenoic acid
Linoleic C18:2 9,12-Octadecadienoic acid
Linolenic C18:3 9,12,15-octadecatrienoic acid
Arachidic C20:0 Eicosanoic acid
Gadoleic C20:l 9-eicosenoic acid
Behenic C22:0 Docosanoic acid
Lignoceric C24:0 Tetracosanoic acid
Table 4.4 : Neat jatropha methyl ester and neat corn methyl ester majorcomponent
fatty acid
Fatty Acid (%) FormulaJME CME
This work Source* This work Source*
Palmitic C16:0 22.45 16.02 22.11 11.54
Stearic C18:0 10.00 10.21 4.09 2.02
Oleic C18:l 8.04 38.54 8.14 28.32
Linoleic C18:2 52.90 33.08 59.06 55.78
Others Cn 6.61 2.15 6.60 2.32
Source*: (Wright & Evans, 2008), (Chiou, 2008)
Table 4.5 shows the fatty acid compositions of the neat biodiesel and biodiesel
blends at Corn methyl ester (CME) Jatropha methyl ester (JME) mass ratio of;
23
i. CME:JME (0:100)
ii. CME:JME (20:80)
iii. CME:JME (40:60)
iv. CME:JME (60:40)
v. CME:JME (80:20)
vi. CME:JME (100:0)
Saturated fatty acid is methyl ester with no double bond. Unsaturated fatty acid is
methyl ester with one double bond or more. Observation from Table 4.5, neat
JME contained more saturated fat than neat CME. Vice-versa, CME contained
more unsaturated fat than the neat JME. The percentage of saturation lessens as
CME mass ratio increased in each blending. In the meantime, the total amount of
monosaturated fat remained the same with little almost no increment or
decrement in the total percentage while, the percentage of polysaturated fat
escalated as the amount CME blend ratio increased.
Table 4.5 : Fatty acid compositions ofJatropha methyl ester(JME) and Cornmethyl ester(CME) with its respective blend ratios
Fatty Acid(%)
FormulaCME :JME
(0:100)20:80 40:60 60:40 80:20
CME:JME
(100:0)
Myristic C14:0 0.28 0.22 0.22 0.21 0.23 0.17
Palmitic C16:0 22.45 22.08 22.24 22.32 22.70 22.11
Palmitoleic C16:l 3.27 2.84 2.31 1.82 1.42 1.14
Margeric C17:0 - 0.39 0.52 0.47 0.45 0.34
Stearic C18:0 10.00 9.19 7.94 6.77 5.42 4.09
Oleic C18:l 8.04 7.63 6.73 7.53 7.49 8.14
Linoleic C18:2 52.90 54.18 55.91 57.18 58.04 59.06
Linolenic C18:3 0.23 0.50 0.20 0.20 0.70 0.24
Arachidic C20:0 1.12 1.22 1.46 1.62 1.92 1.95
Gadoleic C20:l 0.50 0.76 1.01 1.28 1.64 1.86
Behenic C22:0 1.22 0.59 1.03 0.59 - 0.49
Lignoceric C24:0 - 0.40 0.44 - - 0.41
Saturated
(Cn:0) 35.06 34.09 33.85 31.99 30.71 29.57
Monounsatu rated
(Cn:l) 11.81 11.23 10.05 10.63 10.56 11.13
Polyunsaturated(Cn:2,3) 53.13 54.68 56.11 57.38 58.73 59.30
Total 100.00 100.00 100.00 100.00 100.00 100.00
24
4.3 IODINE VALUE
The iodine value is quantified using the EN-14214 calculation method for determination
of the iodine value adapted for biodiesel from the AOCS Recommended practice Cdlc-
85. This method uses the mass percentage of the fatty acid methyl esters and multiplied
it by an assigned weighting factor (Table 4.6). One example calculation is shown as the
following.
Iodine value calculation (EN14214,2003) for CME:JME(100:0),
Iodine value (IV) = mass % fatty acid x weighting factor
= (0.950 x 1.139%) + (0.86 x 8.139%) + (1.732 x 59.055%)
+ (2.616 x 0.241%) + (0.785 x 1.856%)
= 112.45
Table 4.6 : Weighting Factors for Common Fatty Ac(EN 14214:2003;
ids to Determine odine Value
Methyl Ester Formula Factor
Saturated fatty acids Cn:0 0
Palmitoleic C16:l 0.950
Oleic C18:l 0.860
Linoleic C18:2 1.732
Linolenic C18:3 2.616
Gadoleic C20:l 0.785
Erucic C22:l 0.723
Expressed in gram I2/100gram sample, Table 4.7 shows the correlation between the
iodine value and the degree of unsaturation reported in one decimal place. CME:JME is
represented by shortform C:J. Table 4.8 shows the comparison of the iodine value of this
work with existing journal source.
Table 4.7: Fatty acid composition in total of saturated, monounsaturated andpolyunsaturated with iodine value
Fatty Arid (%) C!:J (0:100) 20:80 40:60 60:40 80:20 C:J(100:0)
Saturated (Cn:0) 35.06 34.09 33.85 31.99 30.71 29.57
Monounsaturated (Cn: 1) 11.81 11.23 10.05 10.63 10.56 11.13
Polyunsaturated (Cn:2,3) 53.13 54.68 56.11 57.38 58.73 59.30
Iodine value (gl2/100g) 102.6 105.0 106.1 108.8 111.4 112.5
25
Table 4.8 : Iodine value
Methyl esterIodine value (gl2/100g)
This-work Source*
JME 102.6 96 to 106
CME 112.5 101 to 119.41
Source*:(Wright & Evans, 2008),(Ramos, Fernandez, Casas, Rodriguez, & Perez, 2009)
Iodine value is limited to 120g VlOOg in the European biodiesel standard EN14214. The
limitation of unsaturated fatty acids prevents the formation of deposits when heating
higher unsaturated fatty acids can result in polymerization of glycer ides(Ramos et al.,
2009). Both JME and CME have iodine value below 120 which are 102.6g I2/100g and
112.5g k/lOOg respectively. Iodine value is a measure for degree of unsaturation in
methyl ester. In the table, as more the unsaturation is present, the iodine value increased
as well. The increment of polyunsaturated fatty acid contributes to the increment of
iodine value in this study.
4.4 OXIDATION STABILITY
The European standard EN14112 establishes that the oxidative stability of biodiesel
should be determined at 110°C by the Rancimat method, requiring a minimum value of
6 hours for the induction period. Figure 4.1 shown is Metrohm 873 Biodiesel Rancimat
instrument used to determine the oxidation stability for neat biodiesel and biodiesel
blends.
Figure 4.1 : Metrohm 873 Biodiesel Rancimat
26
The oxidation stability of biodiesel varies significantly depending on the source of
oil/fat from which the biodiesl is derived, processing conditions, contaminants
particularly trace metals, water, radicals and peroxides and storage stability can be
influence by humidity, sunlight, microorganisms, temperature and oxygen(Bart et al.,
2010). Figure 4.2 shows a graph of Induction Period (IP) against the biodiesel blends of
jatropha mass fraction. Biodiesel blend at 0.6 and 0.8 of mass fraction jatropha indicates
CME:JME (40:60) and CME:JME (20:80), respectively. Both blend ratios managed to
achieve the minimum requirement at 6.18 hours and 6.42 hours respectively. The IP
escalated as the degree of saturation increased with the higher amount of JME in the
blends. Since the objective of the study is to maximize the usage of non-edible oil in
biodiesel production, blend ratio at 0.8 mass fraction jatropha or CME:JME (20:80) is
selected to be further improve for cold flow properties.
Oxidation Stability of Jatropha/Corn BiodieselBlend
6.42
5.89
0 0.2 0.4 0.6 0.8
Biodiesel Blends, Mass Fraction Jatropha Methyl Ester
Figure 4.2: Oxidation Stability of Jatropha/Corn Biodiesel Blend
27
6.74
4.5 Cold Fiter Plugging Point
CFPP test calls for cooling a FAME sample at a specified rate and drawing it under
vacuum through a wire mesh filter screen (Knothe et al., 2005). CFPP is then defined as
the lowest temperature at which 20ml of sample safely passes through the filter within
60s (EN 116). An automatic tester ISL FPP 5Gs was used to carry out the determination
of the CFPP at each biodiesel blend ratio and after the addition of CFI. Figure 4.3 shows
the equipment used to test CFPP which is the automatic tester ISL FPP 5Gs.
Figure 4.3 : Automatic tester ISL FPP 5Gs
4.5.1 Improvement of CFPP by blending of JME and CME
Figure 4.4 shows that pure CME has a CFPP value of -4°C which is lower than
pure JME which has a value of -1.2°C. It can be seen that the edible oil has a
better CFPP compared to the inedible JME. At the blend of 20:80 (CME:JME),
it can be observed that the CFPP value lowers from -1.2°C to 2.0 °C. The trend
continues as the mass fraction of CME increased, and the lowest temperature
achieved is -3.7°C for the blend ratio at 80:20 (CME:JME). Methyl ester that
has long chained saturated fatty acids like behenic (C20:0) and Iignolenic(C24:0)
acid tend to have the worse low-temperature properties. Low temperature
properties depend mostly on the saturated fats while the effect of unsaturated
ester is negligible.
28
Cold Filter Plugging Point of JME:CME Blend
-0.50.2 0.4 0.6 0.8
Biodiesel blends, Mass Fraction Corn Methyl Ester
Figure 4.4: CFPP ofJME:CME blend
Although blend ratio at 80:20 (CME:JME) has the lowest CFPP, the oxidation
stability of this blend is 5.89 hours and it did not meet the oxidation stability
requirement. Therefore, the blend 20:80 (CME:JME) with an oxidation stability
of 6.42 hours and CFPP of -2°C is used for the investigation of CFI additive
addition.
4.5.2 Performance of Acrylic Copolymer as Cold Flow Improver (CFI)
Figure 4.5 shows the effect of acrylic copolymer on the CFPP of the 20:80
(CME:JME) blend. Concentration of 0.0mass%, 0.5mass% and 1.0mass% of
acrylic copolymer was added to the blend to observe the changes in temperature.
The maximum allowable amount of additive used in the biodiesel is 1.0mass%.
The result of -3°C was obtained when 0.5mass% was added. When 1.0 mass%
of additive was added, the temperature greatly reduced to -6°C. The function of
the acryclic copolymer as additive is that it significantly reduces growth and
agglomeration rates as temperature drops below cloud point. Acrylic copolymer
behaves by hindering crystal growth, but do not prevent crystal initiation. They
29
have little effect on the temperature at which crystals that has already form. To
be more precise, the additive co-crystallize on the edges of the growing crystal
plates when crystals form, thereby inhibiting the continued agglomeration of the
plate(Bart et al., 2010).
(JWD«>
•O
=
C3•-4)a
5
|8
Effects ofAcrylic Copolymer on CFPP inCMErJME 720:80 blend
Amount of acrylic copolymer, mass %
Figure 4.5: Effectsof Acrylic Copolymer on CFPP in CME:JME/20:80 Blend
30
CHAPTER 5
RECOMMENDATION AND CONCLUSION
As an effort to promote the usage of non-edible oil as feedstock in biodiesel production,
an investigation of the blending of methyl ester from non-edible oils and methyl ester
from edible oil is done. The blend ratio of 20:80 (CME:JME) has achieved an oxidation
stability of 6.42 hour with CFPP of-2°C.
Some critical parameters like oxidation stability, iodine value and CFPP were
succesfully correlated with the methyl ester composition of each biodiesel, according to
the parameter: degree of unsaturation.
In this study, in order to overcome the shortcomings of jatropha-corn biodiesel, acrylic
copolymer is introduced as CFI additive to further reduce the CFPP. It is found out that
the addition of CFI can enhance the cold flow properties of the biodiesel blend and in
this case is the Jatropha-Corn biodiesel. The 20:80 (CME:JME) blend manage to
achieve a reduction of CFPP from -2°C to -6°C after the addition 1.0 mass% of acrylic
copolymer. Acrylic copolymer significantly helps to reduce growth and agglomeration
rates as temperature drops below cloud point. Acrylic copolymer behaves by hindering
crystal growth, co-crystallize on the edges of the growing crystal plates when crystals
form, thereby inhibiting the continued agglomeration of the plate.
More parameters can be further tested to ensure the biodiesel has met the EN14214
standard; such as the cetane number, flash point, water and sediment content as these
parameters are quite crucial in affecting the cold flow properties of biodiesel.
31
REFERENCES
Ayhan, D. (2009). Progress and recent trends in biodiesel fuels. Energy ConversionandManagement, 50(1), 14-34.
Balat, M., & Balat, H. (2008). A critical review of bio-diesel as a vehicular fuel. EnergyConversion and Management, 49(10), 2727-2741.
Barnwal, B. K., & Sharma, M. P. (2005). Prospects of biodiesel production fromvegetable oils in india. Renewable and Sustainable Energy Reviews, 9(A), 363-378.
Bart, J. C. J., Palmeri, N., & Cavallaro, S. (2010). Biodiesel science andtechnology:From soil to oil (Number 7 ed.). Oxford: Woodhead PublishingLimited,CRC Press.
Boshui, C, Yuqiu, S., Jianhua, F., Jiu, W., & Jiang, W. (2010). Effect of cold flowimprovers on flow properties of soybean biodiesel. Biomass and Bioenergy, 34(9),1309-1313.
£aynak, S., Gurii, M., Bicer, A., Keskin, A., & Icingiir, Y. (2009). Biodiesel productionfrom pomace oil and improvement of its properties with synthetic manganeseadditive. Fuel, 88(3), 534-538.
Chiou, B. (2008). Biodiesel from waste salmon oil.
Dantas, M. B., Albuquerque, A. R., Barros, A. K., Rodrigues Filho, M. G., AntoniosiFilho, N. R., Sinfronio, F. S. M., et al. (2011). Evaluation of the oxidative stabilityof corn biodiesel. Fuel, 90(2), 773-778.
Das, L. M., Bora, D. K., Pradhan, S., Naik, M. K., & Naik, S. N. (2009). Long-termstorage stability of biodiesel produced from karanja oil. Fuel, 88(\ 1), 2315-2318.
Echim, C, Maes, J., & Greyt, W. D. (2012). Improvement of cold filter plugging pointof biodiesel from alternative feedstocks. Fuel, 93(0), 642-648.
European Committee for Standardization (CEN). Fatty acid methyl esterfor dieselengines.Requirements and test methods. Brussels, Belgium: EuropeanCommittee for Standardization (CEN); 2003. EN 14214:2003.
Fernandez, C. M., Ramos, M. J., Perez, A., & Rodriguez, J. F. (2010). Production ofbiodiesel from winery waste: Extraction, refining and transesterification of grapeseed oil. Bioresource Technology, 707(18), 7019-7024.
32
Garcia-Perez, M., Adams, T. T., Goodrum, J. W., Das, K. C, & Geller, D. P. (2010).DSC studies to evaluate the impact of bio-oil on cold flow properties and oxidationstability of bio-diesel. Bioresource Technology, 101(15), 6219-6224.
Gui, M. M., Lee, K. T., & Bhatia, S. (2008). Feasibility of edible oil vs. non-edible oilvs. waste edible oil as biodiesel feedstock. Energy, 33(11), 1646-1653.
Gurii, M., Koca, A., Can, O., (^mar, C., & §ahin, F. (2010). Biodiesel production fromwaste chicken fat based sources and evaluation with mg based additive in a dieselengine. Renewable Energy, 35(3), 637-643.
Ibrahim, A. (2012). Renewable energy sources in the egyptian electricity market: Areview. Renewable and Sustainable EnergyReviews, 76(1), 216-230.
Invest Malaysia. Therenewable energy act and opportunities.
Jinglan, H. Uncertainty propagation in life cycle assessment of biodiesel versus diesel:Global warming and non-renewable energy. Bioresource Technology, (0)
Joshi, H. (2011). Biodiesel production using chemical and enzymatic catalysts andimprovement of cold flow properties using additives. (Ph.D., Clemson University).ProQuest Dissertations and Theses,
Joshi, H., Moser, B. R., Toler, J., Smith, W. F., & Walker, T. (2011). Ethyl levulinate: Apotential bio-based diluent for biodiesel which improves cold flow properties.Biomass and Bioenergy, 35(7), 3262-3266.
Keskin, A., Gurii, M., & Altiparmak, D. (2007). Biodiesel production from tall oil withsynthesized mn and ni based additives: Effects of the additives on fuel consumptionand emissions. Fuel, 86(7-8), 1139-1143.
Keskin, A., Giirii, M., & Altiparmak, D. (2008). Influence of tall oil biodiesel with mgand mo based fuel additives on diesel engine performance and emission.Bioresource Technology, 99(\4), 6434-6438.
Kleinova, A., Paligova, J., Vrbova, M., Mikulec, J., & Cvengros, J. (2007). Cold flowproperties of fatty esters. Process Safety and Environmental Protection, 85(5), 390-395.
Knothe, G., Krahl, J., & Van Gerpen, J. (2005). The biodiesel handbook.Champaign,Illinois: AOCS Press.
Leffler, W. L. (2008). Petroleum refining;In non-technical language (4th ed.). U.S.A:Pennwell Corperation.
33
Ma, F., & Hanna, M. A. (1999). Biodiesel production: A review. BioresourceTechnology, 70(1), 1-15.
Mueller, S. A., Anderson, J. E., & Wallington, T. J. (2011). Impact of biofuel productionand other supply and demand factors on food price increases in 2008. BiomassandBioenergy, 35(5), 1623-1632.
Patil, P. D., & Deng, S. (2009). Optimization of biodiesel production from edible andnon-edible vegetable oils. Fuel, 88(7), 1302-1306.
Perez, A., Casas, A., Fernandez, C. M., Ramos, M. J., & Rodriguez, L. (2010).Winterization of peanut biodiesel to improve the cold flow properties. BioresourceTechnology, 707(19), 7375-7381.
Ramos, M. J., Fernandez, C. M., Casas, A., Rodriguez, L., & Perez, A. (2009). Influenceof fatty acid composition of raw materials on biodiesel properties. BioresourceTechnology, 100(\), 261-268.
Sarin, R., Sharma, M., Sinharay, S., & Malhotra, R. K. (2007). Jatropha-Palm biodieselblends: An optimum mix for asia. Fuel, 5(5(10-11), 1365-1371.
Schwab, A. W., Bagby, M. O., & Freedman, B. (1987). Preparation and properties ofdiesel fuels from vegetable oils. Fuel, 65(10), 1372-1378.
Sims, R. E. H., Mabee, W., Saddler, J. N., & Taylor, M. (2010). An overview of secondgeneration biofuel technologies. Bioresource Technology, 101(6), 1570-1580.
Wetzstein, M., & Wetzstein, H. (2011). Four myths surrounding U.S. biofuels. EnergyPolicy, 39(7), 4308-4312.
Wright, H. J., & Evans, A. D. (2008). New research on biofuels. New York: NovaScience Publisher.
34
Sutamsioa ofProgressRepeat
ProjectWo* CottBues
Ptt-EDX
Snltaissjoo ofDraft Repot
Snbcmaiui ofDissemtaa (soft bound)
SnbansHM of TcChmcdPapa
Oral PrwwiutwMi
SnUmsaioa ofProjectDsioaika{Hud Bound)
APPENDIX
APPENDIX A
Al-GANTTCHART
35
t
J4
3 •
cc
u •in
e*
C/>
•->
*
_fi_
Bl) ACID VALUE
Crude Jatropha Curcas L. oil
APPENDIX B
Table Bl: Acidity of Crude Jatropha Curcas L. oil
Trial Condition
Volume of
Titrant used
(ml)
Acid Value
FFA (%)AverageFFA(%)
1
Before titration
(no sample added)8.5
25.16
23.41
After titration
(no sample added)9.1
After titration
(2g of sample added)32
2
Before titration
(no sample added)10.5
21.65After titration
(no sample added)10.8
After titration
(2g of sample added)30.3
Treated Jatropha Curcas L. Oil
Table B2: Acidity for Treated Jatropha Oil
Trial Condition
Volume of
Titrant used
(ml)
Acid Value
FFA (%)AverageFFA(%)
1
Before titration
(no sample added)3.5
0.6600
0.69772
After titration
(no sample added)4.1
After titration
(2g of sampleadded)
7.1
2
Before titration
(no sample added)12.6
0.72943
After titration
(no sample added)12.9
After titration
(2g of sampleadded)
15.8
36
Refined Corn Oil
Table B3: Acidity of Refined Corn Oil
Trial Condition
Volume of
Titrant used
(ml)
Acid Value
FFA (%)AverageFFA(%)
1
Before titration
(no sample added)7.7
0.89776
0.78554
After titration
(no sample added)8.1
After titration
(2g of sample added)8.8
2
Before titration
(no sample added)11
0.67332After titration
(no sample added)14
After titration
(2g of sample added)19.2
37
B2) TEMPERATURE PROFILES FOR NEAT BIODIESEL
Cloud Point
Table B4: Cloud Point Runs
Cloud PointExperimental
JME CME
Runl 3.9 0.1
Run 2 4 0.1
Run 3 4 0.2
Average 4 0.1
Pour Point
Table B5 : Pour Point Runs
Pour PointExperimental
JME CME
Run 1 3 0
Run 2 3 0
Run 3 3 0
Average 3 0
Cold FilterPlugging Point
Table B6 : Cold Filter Plugging Point Runs
CFPPExperimental
JME CME
Run 1 -1.2 -4.1
Run 2 -1.1 -4.0
Run 3 -1.2 -4.0
Average -1.2 -4
38
B3) OXIDATION STABILITY
Oxidation stability data (Conductivity,uS/cm vs Induction Period.hour)
CME:JME 80:20 / 2.75g
CME:JME40:60/3.
• Induction time
a Stability time
CME;JME60:40/3.i
CME:JME 20:80/3.1
m iI I IiiiIiiiiIiiiiiii n Iiiiiiiiii i i i i i I i i i i i i i i i I i i i i I i i i i I i i i i I i i i i I i
0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0
Figure Bl: Comparison ofthe Induction Period of the Blends
60 -: 4.77 /
55 - z
50 - z
45 - z
40 - : /
35 - :
30 - :
25 - : /20 -
- /
15 - z y
10 - z ^^~^
5 - I ____——— -~~~—~~~~~~
1.5 2.0 2.5 3.0 3.5 .5 5.
Figure B2: Induction Period at CME:JME (100:0)
39
4,5 5.0 5.5 6.0 6.5
Figure B3: Induction Period at CME JME (80:20)
Figure B4: Induction Period at CME:JME (60:40)
40
70 -.
6.18 /
60 --
50 --
40 -
30 - /
20 -/
10 -
4 5
Figure B5: Induction Period at CMEJME (40:60)
au - \ 6.42 /
70 -\ /60 -
- /50 - '. /40 -: /
30 -- /
20 -/
10 -: ^—-~~^^Z-i—i—i—i j T i ii j i i i i | i < i i 1 i i i i 1 i i i i 1 i i
1 1 1 1 1 1
5 6
Figure B6: Induction Period at CME:JME (20:80)
41
65 - z 6.74 /
60 - Z /55 - Z
50 - I
45 - z I40 - z I35 - z /L30 -:
25 -: /
20 - : /
15 -
10 -
5 -
n =—i—i—i—i—1—i—i—i—i—1—i—i—i—i—[ j i i i | i i i i 1 i i i i ] i i i 1 1 f 1a -
Figure B7: Induction Period at CMEJME (0:100)
42